CN110183652A - Ultrabranching polyamide-amine, modified ultra-branching polyamide-amide, preparation method and application - Google Patents
Ultrabranching polyamide-amine, modified ultra-branching polyamide-amide, preparation method and application Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The invention discloses a kind of ultrabranching polyamide-amine, modified ultra-branching polyamide-amide, preparation method and applications, belong to petroleum demulsifier field.Its technical solution includes being slowly added to fatty amine into citrate solution, reacts 1-3h at 20-60 DEG C, obtains precursor solution；Precursor solution is added in rotary evaporator, revolving is spin-dried for solvent at 50-70 DEG C, and then, the reaction was continued at such a temperature 3-10h obtains ultrabranching polyamide-amine；Fatty amine is selected from aliphatic diamine or aliphatic polyamine.In terms of the present invention is applied to petroleum demulsifier, solves the problems, such as that energy consumption is high, high production cost for existing over-branched polyamidoamine preparation, have the characteristics that simple production process, production cost are low, demulsification is high-efficient.
Description
Technical field
The invention belongs to petroleum demulsifier field more particularly to a kind of ultrabranching polyamide-amine, modified ultra-branching polyamides
Amine-amine, preparation method and application.
Background technique
(including surfactant, alkali, polymer) technological phase is driven with ternary is entered in oil exploitation technology, petroleum is adopted
Out in liquid in addition to having the characteristics that water content increases, due to the work of surfactant etc. in petroleum deep processing and transportational process
With and oil-in-water type (O/W type) lotion for being formed, or even form Water-In-Oil oil-in (O/W/O type) or water-in-oil-in water
Multiple emulsions such as (O/W/O types), there are a large amount of surfactants on the interface of lotion, reduce the interface of the type lotion
Tension increases its stability, increases its difficulty that is demulsified, and existing polyethers demulsifier cannot effectively carry out the type lotion
Rapidly and efficiently it is demulsified.
Chinese patent 1 (CN105601941A) discloses a kind of polyamide amine dissaving polymer answering as demulsifier
With the polyamide amine dissaving polymer center is ethylenediamine, and end group is amido, and the polyamide amine is hyperbranched
The number average molecular weight distribution of polymer is 6000~12000.The polyamide amine dissaving polymer is effectively mentioned as demulsifier
High demulsification efficiency.
Chinese patent 2 (CN101323662) discloses a kind of Biodegradable hyper branched aliphatic polyester amide and its system
Preparation Method is mixed using citrate and aliphatic diamine according to ratio of molar ratio in the range of 1:0.2 to 1:5, with lemon
1~10wt% of lemon acid total weight ratio addition catalyst simultaneously stirred evenly with reactant, under the conditions of 10~80 DEG C react 1~
7 days, obtain the degradable hyper branched aliphatic polyamide fiber daiamid amine product of white solid.
However, patent 1 is using ethylenediamine as core, it is hyperbranched preparing using toxic organic compound ether as one of reactant
It needing to obtain over-branched polyamidoamine under 120 DEG C or more of hot conditions when daiamid, energy consumption is larger, high production cost,
There are security risks；Patent 2 is using citrate and aliphatic diamine as raw material, and materials safety is high, but it was being reacted
It needs to add catalyst in journey, finally under the conditions of 100~120 DEG C, vacuumizes 12~36h the reaction was continued that white is prepared is solid
The degradable hyper branched aliphatic polyamide fiber daiamid amine product of body shape, it is long that production produces the period.
Summary of the invention
Place in view of the shortcomings of the prior art, the technical problem to be solved by the present invention is to overcome existing hyperbranched poly
Amide amine preparation the problem of energy consumption is high, high production cost, proposes that a kind of simple production process, production cost is low, demulsification is high-efficient
Ultrabranching polyamide-amine, modified ultra-branching polyamide-amide, preparation method and application.
To solve the technical problem, the technical solution adopted by the present invention are as follows:
The present invention provides a kind of preparation methods of ultrabranching polyamide-amine, comprising the following steps:
It is slowly added to fatty amine into citrate solution, 1-3h is reacted at 20-60 DEG C, obtains precursor solution；
The precursor solution is added in rotary evaporator, revolving to solvent is spin-dried at 50-70 DEG C, then, at this
At a temperature of the reaction was continued 3-10h, obtain ultrabranching polyamide-amine；
The fatty amine is selected from aliphatic diamine or aliphatic polyamine.
Preferably, the additional amount molar ratio of the citrate and fatty amine is 1:2-1:4.
Preferably, the citrate is selected from trimethyl citrate, triethyl citrate, three propyl ester of citric acid, citric acid
Any one in tributyl；
The aliphatic diamine is selected from ethylenediamine, 1,2- propane diamine, 1,3- propane diamine, butanediamine, hexamethylene diamine, piperazine, ammonia
Any one in base piperazine；
Any one of the aliphatic polyamine in diethylenetriamine, triethylene tetramine.
The present invention also provides a kind of ultrabranching polyamide-amine preparation side according to any of the above-described technical solution
Ultrabranching polyamide-amine that method is prepared.
The present invention also provides a kind of ultrabranching polyamide-amine as described in the above technical scheme as demulsifier in petroleum
Application in system.
The present invention also provides a kind of preparation methods of modified ultra-branching polyamide-amide, comprising the following steps:
Ultrabranching polyamide-amine as described in the above technical scheme is dispersed in aldehyde aqueous solution, is uniformly mixed, is delayed
It is slow that dialkylamine is added dropwise, 1-4h is reacted at 20-60 DEG C, obtains solution A；
Halogenated epoxy alkane is slowly added dropwise into solution A, reacts 1-4h at 20-100 DEG C, obtains B solution；
Epoxy ring-opening reagent is slowly added dropwise into B solution, reacts 1-4h at 20-60 DEG C, naturally cools to room temperature, obtain
Modified ultra-branching polyamide-amide.
Preferably, the ultrabranching polyamide-amine, aldehyde, dialkylamine, halogenated epoxy alkane, epoxy ring-opening reagent
Additional amount molar ratio is 1:1-2:1-2:1-2:1-2.
Preferably, any one of the aldehyde in formaldehyde, metaformaldehyde or paraformaldehyde；The dialkylamine is selected from
Any one in dimethylamine, diethylamine, di-n-propylamine or dibutyl amine；The halogenated epoxy alkane is selected from epoxychloropropane or epoxy
N-Propyl Bromide；Any one of the epoxy ring-opening reagent in acid, alkali, alcohol compound, the acid compounds are selected from
Hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, formic acid, acetic acid, malonic acid, succinic acid, glutaric acid, any one in adipic acid；The alkali
Class compound is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, ammonia, methylamine, ethamine, propylamine, butylamine, second two
Amine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, polyethylene polyamine, urine
Or any one in thiosemicarbazides；The alcohol compound is selected from methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, hexanol, second two
Alcohol, propylene glycol, butanediol, glycerine, any one in polyethylene glycol.
The present invention also provides a kind of systems of modified ultra-branching polyamide-amide according to any of the above-described technical solution
The modified ultra-branching polyamide-amide that Preparation Method is prepared.
The present invention also provides a kind of modified ultra-branching polyamide-amides as described in the above technical scheme to exist as demulsifier
Application in petroleum system.
Compared with prior art, the beneficial effects of the present invention are:
1, the present invention provides a kind of preparation methods of ultrabranching polyamide-amine, in the case where being not necessarily to catalyst, when shorter
Interior that ultrabranching polyamide-amine is prepared, reaction condition is mild, simple process, and energy consumption is few, at low cost, convenient for industrial metaplasia
It produces；
2, invention further provides a kind of preparation method of modified ultra-branching polyamide-amide, catalyst is not being needed
Under conditions of ultrabranching polyamide-amine is modified, obtain the water-soluble and good modified ultra-branching polyamide-amide of breaking；
3, the present invention also provides the application of the modified ultra-branching polyamide-amide in oil systems, under cryogenic, needle
To O/W type lotion, oil removal rate reaches 99% or more.
Detailed description of the invention
Fig. 1 is ultrabranching polyamide-amine infrared spectrogram that the embodiment of the present invention 2 is prepared；
Fig. 2 is the modified ultra-branching polyamide-amide infrared spectrogram that the embodiment of the present invention 9 is prepared.
Specific embodiment
Below the technical solution in the specific embodiment of the invention will in detail, completely describe.Obviously, described
Embodiment is only the part specific embodiment of the total technical solution of the present invention, and not all embodiment.Based on this hair
Bright total design, those of ordinary skill in the art's every other embodiment obtained, all falls within the scope of protection of the invention.
One aspect of the present invention provides a kind of preparation method of ultrabranching polyamide-amine, comprising the following steps:
S1: being slowly added to fatty amine into citrate solution, reacts 1-3h at 20-60 DEG C, obtains precursor solution；
S2: above-mentioned precursor solution is added in rotary evaporator, and revolving to solvent is spin-dried at 50-70 DEG C, then,
The reaction was continued at this temperature 3-10h, obtains ultrabranching polyamide-amine；
The fatty amine is selected from aliphatic diamine or aliphatic polyamine.In the embodiment, using being originated from bio-based materials
Citric acid ester type is raw material, carries out ester exchange reaction under the conditions of relatively mild with fatty amine, obtains the biology with Amino End Group
New hyperbranched polyamide-amide.Citrate and aliphatic diamine or the polarity prepolymerization of aliphatic polyamine elder generation, obtain two substitution ends
Then the intermediate of amino the intermediate is added in rotary evaporator, under vacuum-pumping conditions, be not necessarily to catalyst, Ji Kefa
Raw self-assembling reaction, obtains ultrabranching polyamide-amine, which is the yellow green with blue-fluorescence performance
Viscous liquid, for example, its synthesis process is as follows:
It should be noted that using citrate and aliphatic two in the preparation method of existing ultrabranching polyamide-amine
Amine mixing, catalysis reaction can just obtain ultrabranching polyamide-amine in 1-7 days under conditions of catalyst.The process not only needs to urge
The participation of agent, simultaneous reactions slowly, long preparation period, it is at high cost.In the present embodiment step S1, in order to improve citrate
Dispersibility improves the reaction efficiency between citrate and fatty amine, citrate is added as a preference, can take
In organic solvent, after mixing, it is slowly added to fatty amine thereto, reacts 1-3h at 20-60 DEG C, it is molten to obtain presoma
Liquid, the organic solvent are selected from methanol or ethyl alcohol.It is not related to toxic solvent in preparation process described in the present embodiment, and in step
In S2, by evaporation, solvent evaporated, asepsis environment-protecting, this method short preparation period, simple process is conducive to the industrialization of product
Synthesis and production.The reason of embodiment defined reaction object is citrate and aliphatic diamine or aliphatic polyamine is lemon
Lemon acid esters is organism-based raw material, from a wealth of sources, cheap, and multiple active groups in its structure；Aliphatic diamine or rouge
Fat race polyamines is the industrial raw materials for producing and applying extensively, has the amino of strong reactivity in its end group, can be mild
Under the conditions of with citric acid ester type occur ester exchange reaction, by control reaction condition appropriate, it is available have hyperbranched knot
Structure and with Amino End Group daiamid substance.Step S1 specifically defines preparation temperature and the time of presoma, forerunner
The preparation temperature of body can also be any point value in 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C and its range, preceding
The preparation time for driving body can also be 2h；Step S2 specifically defines ultrabranching polyamide-amine preparation temperature and time, over-expense
The preparation temperature for changing polyamide-amide can also be any point value in 55 DEG C, 60 DEG C, 65 DEG C and its range, ultrabranching polyamide-
The preparation time of amine can also be any point value in 4h, 5h, 6h, 7h, 8h, 9h and its range.
In a preferred embodiment, 2-3h is reacted at 40-50 DEG C, obtains precursor solution, which is
Two replace the midbody solution of Amino End Group；The precursor solution is rotated at 60-70 DEG C to solvent and is spin-dried for, then, in the temperature
Degree is lower the reaction was continued 3-4h, obtains ultrabranching polyamide-amine.The temperature that the embodiment further defines preparation process is timely
Between, the reason is that, the ultrabranching polyamide-amine being prepared in the temperature and time, and temperature it is higher obtain it is hyperbranched
The grafting rate and the degree of branching of polyamide-amide are higher, while it is contemplated that lemon esters of gallic acid flash temperature >=70 DEG C, in order to guarantee
The safety of industrialized production sets 60-70 DEG C of reaction temperature, and the product obtained under this condition meets subsequent carry out Amino End Group
The requirement of modified 366~460mgKOH/g of amine value.
In a preferred embodiment, the additional amount molar ratio of the citrate and fatty amine is 1:2-1:4.The embodiment
Specifically define that the additional amount molar ratio of citrate and fatty amine, the molar ratio can also be 1:3.The present embodiment is by citric acid
The additional amount molar ratio of ester and fatty amine is limited to 1:2-1:4, the reason is that, being advantageously implemented atom utilization under the molar ratio
Maximization, reduce the discharge of VOCs and meet the needs of green production.When being higher than 1:4 ratio, the dosage of fatty amine is excessive,
It has unreacted fatty amine to have remained in reaction system, forms VOCs, cause environmental pollution, increase processing difficulty.
In a preferred embodiment, the citrate is selected from trimethyl citrate, triethyl citrate, citric acid 3 third
Any one in ester, tributyl citrate；
The aliphatic diamine is selected from ethylenediamine, 1,2- propane diamine, 1,3- propane diamine, butanediamine, hexamethylene diamine, piperazine, ammonia
Any one in base piperazine；
Any one of the aliphatic polyamine in diethylenetriamine, triethylene tetramine.
This embodiment define the types of citrate, aliphatic diamine and aliphatic polyamine, it is to be understood that right
Citrate, aliphatic diamine and aliphatic polyamine cited by the present embodiment can also be those skilled in the art at this
Field combines common sense to pass through other substances for reasonably selecting and adjusting.
Ultrabranching polyamide-amine preparation method according to any of the above-described embodiment that the present invention also provides a kind of
Ultrabranching polyamide-the amine being prepared.Ultrabranching polyamide-the amine is hyperbranched citric acid-based ultrabranching polyamide-amine, is
Yellow green viscous liquid product with blue-fluorescence performance.
Ultrabranching polyamide-amine that the present invention also provides a kind of as described in above-described embodiment is as demulsifier in petroleum body
Application in system.Ultrabranching polyamide-the amine is as demulsifier in petroleum system, having preferable demulsification performance and water-soluble
Property.
Another aspect of the present invention additionally provides a kind of preparation method of modified ultra-branching polyamide-amide, comprising the following steps:
S1: ultrabranching polyamide-amine as described in above-described embodiment is dispersed in aldehyde aqueous solution, is uniformly mixed,
Dialkylamine is slowly added dropwise, reacts 1-4h at 20-60 DEG C, obtains solution A；
S2: halogenated epoxy alkane is slowly added dropwise into solution A, reacts 1-4h at 20-100 DEG C, obtains B solution；
S3: epoxy ring-opening reagent being slowly added dropwise into B solution, reacts 1-4h at 20-60 DEG C, naturally cools to room temperature,
Obtain modified ultra-branching polyamide-amide.
In the embodiment, have the characteristics that reactivity using ultrabranching polyamide-amine Amino End Group, it is any being added without
Under conditions of catalyst, self-catalyzed reaction is carried out as reactant using organic base, end tertiary amine group is generated, then by the end
The quaternized hyperbranched polyamides of hyperbranched citric acid-based for obtaining end group as epoxy group occurs for tertiary amine group and halogenated epoxy alkane
Amine-amine quarternary ammonium salt compound, in open loops such as the reactants for controlling temperature, adding active amino or hydroxyl under the reaction time
Target product can be obtained, for example, its synthesis process is as follows:
Define reaction temperature and time in S1 step, the temperature can also for 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C,
Any point value in 50 DEG C, 55 DEG C and its range, time can also be any point value in 2h, 3h and its range；In S2 step
Define reaction temperature and time, which can also be 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65
DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, any point value in 95 DEG C and its range, the time can also be 2h, 3h and its model
Enclose interior any point value；Reaction temperature and time are defined in S3 step, which can also be 25 DEG C, 30 DEG C, 35 DEG C, 40
DEG C, 45 DEG C, 50 DEG C, any point value in 55 DEG C and its range, the time can also be any point value in 2h, 3h and its range.
In a preferred embodiment, by the ultrabranching polyamide-as described in above-described embodiment, that amine is dispersed in aldehyde is water-soluble
In liquid, it is uniformly mixed, dialkylamine is slowly added dropwise, reacts 2h at 40-50 DEG C, obtains solution A；Halogen is slowly added dropwise into solution A
For epoxyalkane, 2h is reacted at 80-90 DEG C, obtains B solution；It is slowly added dropwise epoxy ring-opening reagent into B solution, 40-50 DEG C
Lower reaction 2h, naturally cools to room temperature, obtains modified ultra-branching polyamide-amide.The embodiment further defines preparation process
Temperature and time, the reason is that, the modified ultra-branching polyamide-amide being prepared in the temperature and time have Amino End Group
With terminal hydroxy group structure, while there is electropositive quaternary ammonium salt structure in its inside configuration, the cation obtained by the experimental design
Modified ultra-branching daiamid, hydrophilic outer end group can promote be demulsified agent molecule quickly reach on oil-water interfaces, sun from
Minor structure can interact with the surfactant of the electronegativity on oil-water interfaces, be conducive to O/W type lotion in room temperature condition
Under, it realizes and quickly, is efficiently demulsified.
In a preferred embodiment, the ultrabranching polyamide-amine, aldehyde, dialkylamine, halogenated epoxy alkane, epoxy group
The additional amount molar ratio of Ring Opening Reagent is 1:1-2:1-2:1-2:1-2.Under the proportion, it is advantageously implemented atom utilization most
Bigization, the discharge for reducing VOCs and the needs for meeting green production.When being higher than 1:2 ratio, the monomer not reacted completely is had
It is remaining to form VOCs in the reaction system, environmental pollution is caused, processing difficulty is increased.
In a preferred embodiment, any one of the aldehyde in formaldehyde, metaformaldehyde or paraformaldehyde；Described two
Any one of alkylamine in dimethylamine, diethylamine, di-n-propylamine or dibutyl amine；The halogenated epoxy alkane is selected from epoxy chlorine
Propane or epoxy bromopropane；Any one of the epoxy ring-opening reagent in acid, alkali, alcohol compound, the acids
Compound is any one in hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, formic acid, acetic acid, malonic acid, succinic acid, glutaric acid, adipic acid
Kind；The alkaloid compound is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, ammonia, methylamine, ethamine, propylamine, fourth
Amine, ethylenediamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, more ethylene
Any one in polyamines, urine or thiosemicarbazides；The alcohol compound be selected from methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, oneself
Alcohol, ethylene glycol, propylene glycol, butanediol, glycerine, any one in polyethylene glycol.The embodiment specifically defines aldehyde, dioxane
The type of base amine, halogenated epoxy alkane and epoxy ring-opening reagent, it is to be understood that for cited by the present embodiment
Aldehyde, dialkylamine, halogenated epoxy alkane and epoxy ring-opening reagent can also be that those skilled in the art combine in this field
Common sense passes through other substances for reasonably selecting and adjusting.
The present invention also provides a kind of preparations of modified ultra-branching polyamide-amide according to any of the above-described embodiment
The modified ultra-branching polyamide-amide that method is prepared.The modified ultra-branching polyamide-amide is that hyperbranched citric acid-based is hyperbranched
Polyamide-amide quaternary ammonium salt.
The modified ultra-branching polyamide-amide that the present invention also provides a kind of as described in above-described embodiment is as demulsifier in stone
Application in oil systems.The modified ultra-branching polyamide-amide is as demulsifier in application, in cryogenic conditions in petroleum system
Under, for O/W type lotion, oil removal rate reaches 99% or more.
In order to become apparent from, to introduce ultrabranching polyamide-amine, modified ultra-branching provided by the embodiment of the present invention in detail poly-
Amide-amine, preparation method and application, are described below in conjunction with specific embodiment.
Embodiment 1
Ultrabranching polyamide-amine preparation method, comprising the following steps:
The trimethyl citrate of 0.1mol is dissolved in 50ml methanol, drips the ethylenediamine of 0.33mol in constant pressure funnel
It adds to and is added in above-mentioned mixed solution, after 45 DEG C are stirred to react 3h, reaction solution is transferred in pear shape bottle, it is true in automatic rotation
On empty evaporimeter, removing solvent methanol is vacuumized, continuation vacuumizes reaction 7h at 70 DEG C, obtains yellow viscous liquid HP-1, amine
Value is 386.98mgKOH/g.
Embodiment 2
Ultrabranching polyamide-amine preparation method, answer the following steps are included:
The triethyl citrate of 0.1mol is dissolved in 50ml methanol, by the divinyl of 0.33mol three in constant pressure funnel
Amine, which is added dropwise to, to be added in above-mentioned mixed solution, and after 25 DEG C are stirred to react 3h, reaction solution is transferred in pear shape bottle, is being revolved automatically
Turn on vacuum evaporator, vacuumize removing solvent methanol, continuation vacuumizes reaction 4h at 50 DEG C, obtains yellow green viscous liquid
HP-2, amine value 439.25mgKOH/g.
Embodiment 3
Ultrabranching polyamide-amine preparation method, answer the following steps are included:
Three propyl ester of citric acid of 0.1mol is dissolved in 50ml methanol, by 1, the 3- of 0.33mol the third two in constant pressure funnel
Amine, which is added dropwise to, to be added in above-mentioned mixed solution, and after 35 DEG C are stirred to react 3h, reaction solution is transferred in pear shape bottle, is being revolved automatically
Turn on vacuum evaporator, vacuumize removing solvent methanol, continuation vacuumizes reaction 3.5h at 60 DEG C, obtains yellow green viscous liquid
HP-3, amine value 426.58mgKOH/g.
Embodiment 4
Ultrabranching polyamide-amine preparation method, answer the following steps are included:
The trimethyl citrate of 0.1mol is dissolved in 50ml methanol, drips the ethylenediamine of 0.33mol in constant pressure funnel
It adds to and is added in above-mentioned mixed solution, after 45 DEG C are stirred to react 3h, reaction solution is transferred in pear shape bottle, it is true in automatic rotation
On empty evaporimeter, removing solvent methanol is vacuumized, continuation vacuumizes reaction 8h at 50 DEG C, obtains ultrabranching polyamide-amine, amine value
For 400.75mgKOH/g.
Embodiment 5
The preparation method of modified ultra-branching polyamide-amide, answer the following steps are included:
By the HP-1 (amine value calculating) of 0.1mol be dispersed in containing 0.1mol formalin (mass concentration 37%~
40%, commercially available analysis is pure) in, it is uniformly mixed, 0.1mol dimethylamine (mass concentration 33%, commercially available analysis are pure), control is slowly added dropwise
Mixeding liquid temperature processed reacts 2h, obtains clear solution between 50 DEG C.
0.1mol epoxychloropropane (mass concentration 99%, commercially available analysis are pure), control are slowly added dropwise into above-mentioned mixed liquor
Mixeding liquid temperature reacts 2h at 90 DEG C.
0.1mol ethylenediamine (mass concentration 99%, commercially available analysis are pure), control mixing are slowly added dropwise into above-mentioned mixed liquor
Liquid temperature reacts 2h between 40 DEG C.
Room temperature is naturally cooled to, hyperbranched citric acid-based polyamide-amide quaternary ammonium salt is obtained.
Embodiment 6
The preparation method of modified ultra-branching polyamide-amide, answer the following steps are included:
By the HP-1 (being calculated according to amino) of 0.1mol be dispersed in 0.1mol formalin (mass concentration 37%~
40%, commercially available analysis is pure) in, it is uniformly mixed, 0.1mol dimethylamine (mass concentration 33%, commercially available analysis are pure), control is slowly added dropwise
Mixeding liquid temperature processed reacts 2h, obtains clear solution between 40 DEG C.
0.1mol epoxychloropropane (mass concentration 99%, commercially available analysis are pure), control are slowly added dropwise into above-mentioned mixed liquor
Mixeding liquid temperature reacts 2h at 80 DEG C.
0.1mol diethylenetriamine (mass concentration 99%, commercially available analysis are pure), control are slowly added dropwise into above-mentioned mixed liquor
Mixeding liquid temperature reacts 2h between 50 DEG C.
Room temperature is naturally cooled to, hyperbranched citric acid-based polyamide-amide quaternary ammonium salt is obtained.
Embodiment 7
The preparation method of modified ultra-branching polyamide-amide, answer the following steps are included:
By the HP-1 (being calculated according to amino) of 0.1mol be dispersed in 0.1mol formalin (mass concentration 37%~
40%, commercially available analysis is pure) in, it is uniformly mixed, 0.1mol dimethylamine (mass concentration 33%, commercially available analysis are pure), control is slowly added dropwise
Mixeding liquid temperature processed reacts 2h, obtains clear solution between 45 DEG C.
0.1mol epoxychloropropane (mass concentration 99%, commercially available analysis are pure), control are slowly added dropwise into above-mentioned mixed liquor
Mixeding liquid temperature reacts 2h at 85 DEG C.
0.1mol triethylene tetramine (mass concentration 99%, commercially available analysis are pure), control are slowly added dropwise into above-mentioned mixed liquor
Mixeding liquid temperature reacts 2h between 45 DEG C.
Room temperature is naturally cooled to, hyperbranched citric acid-based polyamide-amide quaternary ammonium salt is obtained.
Embodiment 8
The preparation method of modified ultra-branching polyamide-amide, answer the following steps are included:
By the HP-2 (being calculated according to amino) of 0.1mol be dispersed in 0.1mol formalin (mass concentration 37%~
40%, commercially available analysis is pure) in, it is uniformly mixed, 0.1mol dimethylamine (mass concentration 33%, commercially available analysis are pure), control is slowly added dropwise
Mixeding liquid temperature processed reacts 2h, obtains clear solution between 48 DEG C.
0.1mol epoxychloropropane (mass concentration 99%, commercially available analysis are pure), control are slowly added dropwise into above-mentioned mixed liquor
Mixeding liquid temperature reacts 2h at 83 DEG C.
0.1mol ethylenediamine (mass concentration 99%, commercially available analysis are pure), control mixing are slowly added dropwise into above-mentioned mixed liquor
Liquid temperature reacts 2h between 46 DEG C.
Room temperature is naturally cooled to, hyperbranched citric acid-based polyamide-amide quaternary ammonium salt is obtained.
Embodiment 9
The preparation method of modified ultra-branching polyamide-amide, answer the following steps are included:
By the HP-2 (being calculated according to amino) of 0.1mol be dispersed in 0.1mol formalin (mass concentration 37%~
40%, commercially available analysis is pure) in, it is uniformly mixed, 0.1mol dimethylamine (mass concentration 33%, commercially available analysis are pure), control is slowly added dropwise
Mixeding liquid temperature processed reacts 2h, obtains clear solution between 44 DEG C.
0.1mol epoxychloropropane (mass concentration 99%, commercially available analysis are pure), control are slowly added dropwise into above-mentioned mixed liquor
Mixeding liquid temperature reacts 2h at 87 DEG C.
0.1mol n-propylamine (mass concentration 99%, commercially available analysis are pure), control mixing are slowly added dropwise into above-mentioned mixed liquor
Liquid temperature reacts 2h between 48 DEG C.
Room temperature is naturally cooled to, hyperbranched citric acid-based polyamide-amide quaternary ammonium salt is obtained.
Embodiment 10
The preparation method of modified ultra-branching polyamide-amide, answer the following steps are included:
By the HP-2 (being calculated according to amino) of 0.1mol be dispersed in 0.1mol formalin (mass concentration 37%~
40%, commercially available analysis is pure) in, it is uniformly mixed, 0.1mol dimethylamine (mass concentration 33%, commercially available analysis are pure), control is slowly added dropwise
Mixeding liquid temperature processed reacts 2h, obtains clear solution between 43 DEG C.
0.1mol epoxychloropropane (mass concentration 99%, commercially available analysis are pure), control are slowly added dropwise into above-mentioned mixed liquor
Mixeding liquid temperature reacts 2h at 82 DEG C.
0.1mol lauryl amine (mass concentration 99%, commercially available analysis are pure), control mixing are slowly added dropwise into above-mentioned mixed liquor
Liquid temperature reacts 2h between 49 DEG C.
Room temperature is naturally cooled to, hyperbranched citric acid-based polyamide-amide quaternary ammonium salt is obtained.
Embodiment 11
The preparation method of modified ultra-branching polyamide-amide, answer the following steps are included:
By the HP-3 (being calculated according to amino) of 0.1mol be dispersed in 0.1mol formalin (mass concentration 37%~
40%, commercially available analysis is pure) in, it is uniformly mixed, 0.1mol dimethylamine (mass concentration 33%, commercially available analysis are pure), control is slowly added dropwise
Mixeding liquid temperature processed reacts 2h, obtains clear solution between 42 DEG C.
0.1mol epoxychloropropane (mass concentration 99%, commercially available analysis are pure), control are slowly added dropwise into above-mentioned mixed liquor
Mixeding liquid temperature reacts 2h at 84 DEG C.
0.1mol octadecylamine (mass concentration 90%, commercially available analysis are pure), control mixing are slowly added dropwise into above-mentioned mixed liquor
Liquid temperature reacts 2h between 43 DEG C.
Room temperature is naturally cooled to, hyperbranched citric acid-based polyamide-amide quaternary ammonium salt is obtained.
Embodiment 12
The preparation method of modified ultra-branching polyamide-amide, answer the following steps are included:
By the HP-3 (being calculated according to amino) of 0.1mol be dispersed in 0.1mol formalin (mass concentration 37%~
40%, commercially available analysis is pure) in, it is uniformly mixed, 0.1mol dimethylamine (mass concentration 33%, commercially available analysis are pure), control is slowly added dropwise
Mixeding liquid temperature processed reacts 2h, obtains clear solution between 41 DEG C.
0.1mol epoxychloropropane (mass concentration 99%, commercially available analysis are pure), control are slowly added dropwise into above-mentioned mixed liquor
Mixeding liquid temperature reacts 2h at 89 DEG C.
0.1mol polyethylene glycol (mass concentration 99%, commercially available analysis are pure) is slowly added dropwise into above-mentioned mixed liquor, control is mixed
Liquid temperature is closed between 47 DEG C, reacts 2h.
Room temperature is naturally cooled to, hyperbranched citric acid-based polyamide-amide quaternary ammonium salt is obtained.
Comparative example 1
The preparation method is the same as that of Example 1 for ultrabranching polyamide-amine, the difference is that, in automatic rotary vacuum evaporator
On, under the conditions of 40 DEG C, vacuumize process is carried out to it, obtains ultrabranching polyamide-amine presoma, amine value is
560.72mgKOH/g。
Comparative example 2
The preparation method of modified ultra-branching polyamide-amide, answer the following steps are included:
Commercially available ultrabranching polyamide-amine (trade mark W301) of 0.1mol is dispersed in water-soluble containing 0.1mol formaldehyde
In liquid (mass concentration 37%~40%, commercially available analysis are pure), it is uniformly mixed, 0.1mol dimethylamine (mass concentration is slowly added dropwise
33%, commercially available analysis is pure), mixeding liquid temperature is controlled between 50 DEG C, is reacted 2h, is obtained clear solution.
0.1mol epoxychloropropane (mass concentration 99%, commercially available analysis are pure), control are slowly added dropwise into above-mentioned mixed liquor
Mixeding liquid temperature reacts 2h at 90 DEG C.
0.1mol ethylenediamine (mass concentration 99%, commercially available analysis are pure), control mixing are slowly added dropwise into above-mentioned mixed liquor
Liquid temperature reacts 2h between 40 DEG C.
Room temperature is naturally cooled to, hyperbranched citric acid-based polyamide-amide quaternary ammonium salt is obtained.
Performance test
Hyperbranched citric acid-based polyamide-amide and embodiment 5-12 that embodiment 1-4, comparative example 1 are prepared, comparison
Hyperbranched citric acid-based polyamide-amide quaternary ammonium salt that example 2 is prepared and it is commercially available demulsifier CW-01 it is quaternary ammonium salt-modified
Commercially available ultrabranching polyamide-amine (trade mark W301) that polyethers demulsifier, comparative example 2 are used carries out demulsification at room temperature
Test, wherein commercially available demulsifier CW-01 is that the structure of quaternary ammonium salt-modified polyethers demulsifier is as follows:
R and R ' is the alkane of monovalence, and R " is alkane or hydrogen, and m and n are the integer greater than 0, and test result is as follows:
| Sample | Dosage | Be demulsified temperature | It is demulsified the time | Oil removal rate |
| CW-01 | 80ppm | Room temperature | 10min | > 94% |
| W301 | 80ppm | Room temperature | 10min | 60% |
| Embodiment 1 | 80ppm | Room temperature | 10min | > 97% |
| Embodiment 2 | 80ppm | Room temperature | 10min | > 97% |
| Embodiment 3 | 80ppm | Room temperature | 10min | > 97% |
| Embodiment 4 | 80ppm | Room temperature | 10min | > 97% |
| Embodiment 5 | 80ppm | Room temperature | 10min | > 97% |
| Embodiment 6 | 80ppm | Room temperature | 10min | > 99% |
| Embodiment 7 | 80ppm | Room temperature | 10min | > 99% |
| Embodiment 8 | 80ppm | Room temperature | 10min | > 99% |
| Embodiment 9 | 80ppm | Room temperature | 10min | > 99% |
| Embodiment 10 | 80ppm | Room temperature | 10min | > 99% |
| Embodiment 11 | 80ppm | Room temperature | 10min | > 99% |
| Embodiment 12 | 80ppm | Room temperature | 10min | > 99% |
| Comparative example 1 | 80ppm | Room temperature | 10min | 34% |
| Comparative example 2 | 80ppm | Room temperature | 10min | > 97% |
The hyperbranched lemon that the hyperbranched citric acid-based polyamide-amide and embodiment 9 be prepared to embodiment 2 is prepared
Lemon acid-based polyamide-amine quaternary ammonium salt carries out infrared spectrum analysis, the result is shown in Figure 1, Fig. 2.Such as Fig. 1 it can be found that in 3286cm-1It is attached
Closely there is the absorption by force of amino bimodal, and in 1700cm-1The absorption peak of left and right ester group is changed into 1654cm-1Amido bond absorption
Peak, this illustrates that fatty amine replaces the ester group in citrate completely, and hyperbranched citric acid-based polyamide-has been prepared
Amine.By Fig. 2 it can be found that compared to Figure 1, in 3286cm-1Nearby there is the absorption by force of amino is bimodal to become 3402cm-1Strong suction
Broad peak is received, this explanation has terminal hydroxy group and Amino End Group structure simultaneously in this configuration, in addition, in 1650cm-1The intensity of absorption peak
It is slightly changed, these data explanation, the quaternary ammonium salt for completing hyperbranched citric acid-based polyamide-amide under these experimental conditions changes
Property.There is more active groups and good hydrophily by modified quaternary ammonium salt structure, be conducive to the agent material that is demulsified, more
It is accessible to oil-water separation interface, realizes the rapidly and efficiently demulsification of O/W type lotion at room temperature.
Claims (10)
1. ultrabranching polyamide-amine preparation method, which comprises the following steps:
It is slowly added to fatty amine into citrate solution, 1-3h is reacted at 20-60 DEG C, obtains precursor solution；
The precursor solution is added in rotary evaporator, revolving to solvent is spin-dried at 50-70 DEG C, then, in the temperature
Lower the reaction was continued 3-10h, obtains ultrabranching polyamide-amine；
The fatty amine is selected from aliphatic diamine or aliphatic polyamine.
2. the preparation method of ultrabranching polyamide-amine according to claim 1, which is characterized in that the citrate and
The additional amount molar ratio of fatty amine is 1:2-1:4.
3. the preparation method of ultrabranching polyamide-amine according to claim 1 or 2, which is characterized in that the citrate
Any one in trimethyl citrate, triethyl citrate, three propyl ester of citric acid, tributyl citrate；
The aliphatic diamine is selected from ethylenediamine, 1,2- propane diamine, 1,3- propane diamine, butanediamine, hexamethylene diamine, piperazine, amino piperazine
Any one in piperazine；
Any one of the aliphatic polyamine in diethylenetriamine, triethylene tetramine.
4. the hyperbranched poly that the preparation method of ultrabranching polyamide-amine according to claim 1-3 is prepared
Amide-amine.
5. application of the ultrabranching polyamide-amine according to claim 4 as demulsifier in petroleum system.
6. a kind of preparation method of modified ultra-branching polyamide-amide, which comprises the following steps:
Ultrabranching polyamide-amine as claimed in claim 4 is dispersed in aldehyde aqueous solution, is uniformly mixed, is slowly added dropwise
Dialkylamine reacts 1-4h at 20-60 DEG C, obtains solution A；
Halogenated epoxy alkane is slowly added dropwise into solution A, reacts 1-4h at 20-100 DEG C, obtains B solution；
Epoxy ring-opening reagent is slowly added dropwise into B solution, reacts 1-4h at 20-60 DEG C, naturally cools to room temperature, be modified
Ultrabranching polyamide-amine.
7. the preparation method of modified ultra-branching polyamide-amide according to claim 6, which is characterized in that described hyperbranched
Polyamide-amide, aldehyde, dialkylamine, halogenated epoxy alkane, epoxy ring-opening reagent additional amount molar ratio be 1:1-2:1-2:1-
2:1-2。
8. the preparation method of modified ultra-branching polyamide-amide according to claim 6 or 7, which is characterized in that
Any one of the aldehyde in formaldehyde, metaformaldehyde or paraformaldehyde；
Any one of the dialkylamine in dimethylamine, diethylamine, di-n-propylamine or dibutyl amine；
The halogenated epoxy alkane is selected from epoxychloropropane or epoxy bromopropane；
Any one of the epoxy ring-opening reagent in acid, alkali, alcohol compound, the acid compounds are selected from salt
Acid, sulfuric acid, acetic acid, oxalic acid, formic acid, acetic acid, malonic acid, succinic acid, glutaric acid, any one in adipic acid；The bases
Compound be selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, ammonia, methylamine, ethamine, propylamine, butylamine, ethylenediamine,
Propane diamine, butanediamine, pentanediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, polyethylene polyamine, urine or
Any one in thiosemicarbazides；The alcohol compound be selected from methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, hexanol, ethylene glycol,
Propylene glycol, butanediol, glycerine, any one in polyethylene glycol.
9. the modification being prepared according to the preparation method of the described in any item modified ultra-branching polyamide-amides of claim 6-8
Ultrabranching polyamide-amine.
10. application of the modified ultra-branching polyamide-amide according to claim 9 as demulsifier in petroleum system.
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